Lubricating composition



United States Patent Oflice 3,389,082 Patented June 18, 1968 3,389,682 LUBRICATHNG CGMPUSETKGN haui M. Kerschuer, Trenton, and Frederick G. Hess,

Cranhury, NJ assignors to Cities Service Oil Company, a corporation of Delaware No Drawing. Original application Mar. 6, 1964, Ser. No. 356,123,, new Patent No. 3,338,935, dated Aug. 29, W67. Divided and this application Aug. 17, 1%7, Ser.

No. amass 9 Claims. (Ci. ass-s25 ABSTRACT 9F THE DISCLOSURE A lubricating composition having a substantial quantity of a lubricant base material and a minor quantity of an amine salt of a metal (acid hydrocarbyl orthophosphate) wherein the metal is a Group iV-B metal of the periodic table.

CROSS-REFERENCE TO R LATED APPLICATION This application is a division of application Ser. No. 350,121 filed Mar. 6, 1964, now Patent No. 3,338,935.

This invention relates to novel metal organo orthophosphates, novel amine salts of such orthophosphates and to hydrocarbon compositions containing the amine salts. The novel metal orsano orthophosphates are certain metal (acid hydrocarbyl orthophosphates).

Normally liquid hydrocarbon products such as fuels and lubricating oils contain additives for improving their performance characteristics. Thus, in fuels such as gasoline, additives are employed for improving various performance characteristics such as to assist in maintaining cleanliness of the carburetor, to resist surface ignition, and to inhibit rust and carburetor icing. Lubricating compositions contain various additives such as those for improving viscosity index and lubricity. The additives vary in effectiveness and it is often necessary to use a number of additives in a single composition.

It has now been found that amine salts of certain metal (acid hydrocarbyl orthophosphates) are beneficial in imparting carburetor and intake system detergency, inhibi tion of rust, and inhibition of carburetor icing, reduction in octane requirement increase, and resistance to surface ignition of liquid hydrocarbon fuels. Also, the amine ad ducts are good anti-Wear agents for use in lubricants.

The novel amine salts of this invention are amine neutralization products of acid hydrocarbyl orthophosphates of a Group lV-B metal of the Periodic Table. A suitable Periodic Table is shown on page 336 of the Handbook of Chemistry and Physics, Thirty-first Edition (1949). The metal (acid hydrocarbyl orthophosphate) intermediates of this invention can be represented by the formula:

wherein M is a Group IV-B metal such as titanium, zirconium of hafnium; n is an integer from 1 to 4; n is an integer from t) to 3; the total of n and n is equal to the valence of the metal M; and each R is a hydrocarbon group such as one having from 1 to about 30 carbon atoms. The metal as represented by M in the above generic Formula I can be trivalent or tetravalent. It is preferred that M represent tetravalent titanium. it can be seen from Formula I that the metal (acid hydrocarbyl orthophosphates) and their corresponding amine salts which are also referred to herein as ammonium derivatives, amine adducts or simply additives, can have 1, 2, 3, or 4 acid groups (OH) per metal atom. Also, the total number of. carbons can vary from about 4 to over 100,

and preferably from about 4 to about 60 carbon atoms. Preferably, the intermediate metal (acid hydrocarbyl orthophosphates) contain 2 or 4 acid groups, and can be represented by the following generic formulae respectively:

wherein R represents hydrocarbyl having from 1 to about 30 carbon atoms and M is tetravalent titanium or zirconium.

The intermediate compounds of Formula I, i.e. the metal (acid hydrocarbyl orthophosphates) prior to neutralization of an acid group with an amine can be prepared by reacting a hydrocarbyl diacid orthophosphate which can be represented by the formula: PO(OR) (OI-D wherein R represents hydrocarbyl as in Formula I, or a mixture of a hydrocarbyl diacid orthophosphate and a di(hydrocarbyl) mono acid orthophosphate with a halide of a Group lVB metal of the Periodic Table dispersed or dissolved in an inert organic solvent. The di(hydrocarbyl) mono acid orthophosphate can be represented by the formula: PO(OR) (OH). The intermediates of this invention can also be prepared by reacting a hydroxy compound, e.g., alkanol, alkenol, or phenol with a Group IV-B metal halide and phosphorus pentoxide. This process permits direct synthesis of the intermediates from raw starting materials.

Illustrative of halides of Group IV-Bl metals there can be mentioned: titanium trichloride; titanium tetrachloride; zirconium tetrachloride; zirconium trichloride; titanium tetrabromide; hafnium tetrachloride; and the like. The reaction temperatures are preferably from about 40 C. to about 110 C. and particularly from about C. to about C. About 3 or about 4 moles of the orthophosphate are reacted with each mole of the: halide depending on whether the metal is in the trivalent or tetravalent state respectively. However, the molar ratio of the reactants can Vary over a Wide range, e.g. in reacting the tetrahalides with a diacid mono (hydrocarbyl) orthophosphate or a mixture of the diacid and monoacid reactants about 3 to about 5 moles of the orthophosphate can be employed per mole of the tetrahalide. The inert solvent is preferably a hydrocarbon such as an aliphatic or aromatic hydrocarbon, c.g. benzene, toluene, heptane, octane, hexane, etc. However, the inert organic solvent need not be hydrocarbon, but instead any inert organic solvent such as an ether or halogenated hydrocarbon cg. ethyl ether, tetrahydrofuran, carbon tetrachloride, chlorobenzene, etc. can be employed.

In the above reaction wherein the phosphate reactant is a mixture containing both one and two acid groups per molecule, it is preferred that at least 10% by weight and refcrably at least 40% by weight of the mixture of orthophosphates be that of diacid mono (hydrocarbyl) orthophosphate since the monoacid dihydrocarbyl orthophosphates when reacted with the metal halides give compounds without a free acid group and therefore cannot be neutralized with an amine. Illustratively the reaction of a diacid n1ono(hydrocarby1) orthophosphate with titanium tetrachloride to prepare a titanium tetra[mon0acid monothydrocarbyl)orthophosphate] can be shown by the equation:

wherein R is hydrocarbon having from 1 to about 30 carbon atoms.

Use of a mixture of a diacid mono (hydrocarbyl) orthophosphate and mono acid di(hydrocarbyl) orthophosphate reactants with the metal reactants produces a mixture of products wherein some of the phosphate groups 3 do not have four free hydroxyl groups but instead have less than four acid groups including a portion of the reaction product having no acid groups, e.g. a titanium tetra [di(hydrocarbyl) orthophosphate].

In addition to the compounds as represented by Formula I herein and those without a free acid group as can be produced by using the dihydrocarbyl orthophosphate reactant, the reaction mixture often contains minor quantities of additional compounds not all of which have been entirely identified, including compounds wherein both acid groups of one or more of the diacid monohydrocarbyl orthophosphates become bound directly to the metal such as those of the following formula wherein one of the phosphate groups is bound to a tetravalent metal through two oxygen groups:

wherein M is a metal as hereinbefore described and each R is hydrocarbyl having 1 to about 30 carbon atoms. However, the mixture of compounds produced in the reaction can be neutralized with an amine without separation of the individual metal compounds or complexes and can be employed as additives to hydrocarbon fuels, e.g. gasoline, or lubricants. Also, it is not necessary, although generally desirable, to separate the metal compounds produced in the reaction or their amine salts from the solvent prior to use.

The amine employed in preparing the additives of this invention can be any salt forming organic amine such as one having from 1 to about 30 carbon atoms. The amine can be primary, secondary or tertiary, aliphatic aromatic or alicyclic. The cyclic amines can be carbocyclic or heterocyclic. The amine can be a mono-, di-, trior other polyamine. The aliphatic amines as well as the aromatic and alicyclic amines can be those of hydrocarbons or bydrocarbons carrying various substitutes such as hydroxyl groups.

The following formulae illustrate various preferred amines which can be employed in this invention:

IH-N-R and RLN- o in n-N-IU (b) 1'1 R wherein R is hydrocarbon, each R and R is hydrogen or hydrocarbon, n is an integer from 2 to about and the total number of carbon atoms in each amine is from 1 to about 30. Preferably R is aliphatic hydrocarbyl and each R and R is hydrogen or aliphatic hydrocarbyl. The aliphatic hydrocarbyl is preferably alkyl or alkenyl and particularly one having from 6 to about 24 carbon atoms.

Illustrative of suitable amines for neutralizing the metal (acid hydrocarbyl orthophosphates) there can be mentioned: methylamine; ethylamine; diethylamine; propylamine; tripropylamine; isopropylarnine; butylamine; isobutylarnine; hexylamine; 2-ethylhexylamine; octylamine; dodecylamine; 2-propyldecylamine; pentadecylamine; tetradecylamine; octadecylamine; 6 butyloctadecylamine; eicosamine; 6,6-dirnethyl-8-propyldecylamine; S-hexyl-lO- isobutyloctadecylamine; dioctylamine; tribenzylamine; hexadecylamine; decylamine; N-hexyloctylamine; N,N-dimethyldodecylamine; oleylamine; linoleylamine'; 1,10-de amethylenediamine; ethylenediamine; 1,2 propylencdiamine; 1,12 dodecamethylenediamine; tetramethylenediamine; 1,6 hexamethylenediamine; triethylenetetramine; 1,2-phenylenediamine; benzylamine; 3,3-biphenyldiamine; 3-biphenylamine; l-naphthylamine; l-fluoroenamine; aniline; N-methylaniline; N,N-dimethylaniline; 2,3-phenylenediamine; Z-furanamine; piperazine; piperidine; furfurylamine; N-cyclohexylheptylamine; and the like. The amines can also contain various substituents on the hydrocarbon portion such as hydroxyl groups, e.g. alkanolamines, such as diethanolamine; 3,3-hydroxydipropanolamine; isopropanolamine, and the like.

The hydrocarbyl radical attached to the phosphate can be aliphatic, aromatic, 0r cycloaliphatic, e.g., alkyl, alkenyl, aryl, aralkyl, alkaryl, etc. The aliphatic group can be saturated or unsaturated, e.g. containing mono-, di-, or polyolefinic unsaturation. The hydrocarbon group as represented by R in Formula Ican also contain various substituents such as halogen groups.

Illustrative of the diacid mono (hydrocarbyl) phosphates and monoacid di(hydrocarbyl) orthophosphate reactants there can be mentioned: diacid mono(octyl) orthophosphate; diacid mono(lauryl) orthophosphate; monoacid ethyl amyl orthophosphate; monoacid tertiary butyl isoamyl orthophosphate; di(Z-ethylhexyl) monoacid orthophosphate; diacid mono (Z-ethylhexyl) orthophosphate; diacid mono(n-octyl) orthophosphate; diacid mono(isooctyl) orthophosphate; monoacid isoamyl isooctyl orthophosphate; diacid mono (nonyl) orthophosphate; monoacid di(nonyl) orthophosphate; monoacid methyl nonyl orthophosphate; diacid mono (cetyl) orthophosphate; diacid mono (tetradecyl) orthophosphate; diacid mono(stearyl) orthophosphate; monoacid di(eicosyl) orthophosphate; and diacid mono(eicosyl) orthophosphate. Illustrative of unsaturated aliphatic orthophosphates there can be mentioned: diacid mono (oleyl) orthophosphate; mono acid di(oleyl) orthophosphate; monoacid di(linoleyl) orthophosphate; monoacid oleyl lauryl orthophosphate; diacid mono (linoleyl) orthophosphate; monoacid ethyl linoleyl orthophosphate; diacid mono (4-heptenyl) orthophosphate; diacid mono (6 decanyl) orthophosphate; and the like. Illustrative of the phosphate reactant having an aryl group there can be mentioned those of phenyl, naphthyl and their substituted derivatives such as: monoacid di(benzyl) orthophosphate; diacid mono (benzyl) orthophosphate; monoacid ethyl benzyl orthophos phate; monoacid octyl phenyl orthophosphate; diacid mono (phenyl) orthophosphate; monoacid lauryl phenyl orthophosphate; monoacid di(naphthyl) orthophosphate; diacid mono (naphthyl) orthophospbate; diacid mono (cresyl) orthophosphate; monoacid di(cresyl) orthophosphate; diacid mono (Xylyl) orthophosphate; diacid mono (Z-ethylphenyl) orthophosphate; and the like. Illustrative of phosphate reactants having a cycloaliphatic group there can be mentioned: monoacid di(cycloheptyl) ortho phosphate; diacid mono (cycloheptyl) orthophosphate; monoacid di(ethylcycloheptyl) orthophosphate; diacid mono(cyclopentyl) orthophosphate; and the like.

The amine salts can be prepared by simply neutralizing the free acid group or groups of the metal (acid hydrocarbyl orthophosphates). Formation of the adduet can take place at room temperature although somewhat elevated temperatures such as that of about F. is preferred. Preferably each of the acid groups of the orthophosphate is neutralized with basic nitrogen of the amine reactant, although this is not necessary. Neutralization can be accomplished by simply adding the amine to raise the pH from less than about 5, of the unneutralized compounds up to a pH of at least 6 or 7. Also, the neutralization can be accomplished by adding a stciehiometric quantity of the amine to the particular metal (acid hydrocarbyl orthophosphate). Illustratively in the case of using a monoamine such as oleyl amine and neutralizing all the acid groups the amine adducts of this invention can be represented by the formula:

wherein M is a Group IV-B metal; R is a hydrocarbyl having from 1 to about 30 carbon atoms; A is an amine; IL is an integer from i to 4; n is an integer from 0 to 3 and the total of n and n is equal to the valence of the metal M.

The novel amine salts of this invention are useful as additives in liquid hydrocarbon compositions since they serve as lubricant additives, anti'corrosion additives, antiicing additives, detergents, anti-stall additives, and reduce octane requirement increase of gasoline. For such use it is preferred that the hydrocarbyl portion of the orthophosphate have at least 6 carbon atoms, such as 6 to 22 carbon atoms and particularly wherein the hydrocarbon group is branched, e.g. Z-ethylhexyl or 4-octylphenyl. Also, for such use it is preferred that the amine have at least 6 carbon atoms such as 6 to 24 carbon atoms, and particularly that the amine be that of an alkyl or alkenyl group which can be a monoor diamine. The quantity of the novel amine salts in various compositions can vary over a wide range depending on the particular base stock to which they are added and their intended purpose. Thus, they can vary from about parts per million by weight of the composition to over 10% by weight of the composition. The hydrocarbon compositions can be prepared by simply dissolving the amine salts in the hydrocarbon.

The novel amine salts are especially useful as gasoline additives to impart their above described properties. The gasoline composition can be either leaded or unleaded. Leaded gasoline is preferred. Thus in accordance with a preferred embodiment of the invention a gasoline composition is provided which comprises a major portion of leaded hydrocarbon base fuel boiling in the gasoline range and containing between about 10 to about 500 parts per million (ppm) by weight, of the novel amine salts, preferably from about to about 250 ppm. and particularly from about 25 to 200 ppm. In addition to gasoline, the amine salts can be added to other hydrocarbon fuels in minor quantities such as in diesel oil to impart antirust activity, etc. to the composition. By the term gasoline, hydrocarbon base fuel boiling in the gasoline range and similar terms is meant a petroleum fraction boiling in the gasoline boiling range (e.g. between about 50 F. and about 450 F.). The term leaded gasoline refers to gasoline to which there has been added a small amount, such as between 0.1 and about 6.0 ml. per gallon of a metallo-organic antilcnoclr compound such as tetraethyl lead (TEL), tetramethyl lead (TML), tetraisopropyl, etc.

In addition to the novel amine salts and optionally the lead antiknock compounds the gasoline compositions of this invention can include, for instance, light hydrocarbon lubricating oils having viscosities at 100 F. of between about 50 and about 200 Saybolt Universal seconds (SUS) and viscosity indexes of between about and about 120. Such oils may be present in suitable amounts such as be tween about 0.1 and about 1.0 percent by weight of the gasoline composition.

When employed in lubricating compositions such as lubricating oils the novel amine salts improve the boundary lubrication properties of the composition. Thus, lubricants containing the novel amine salts of this invention inhibit stick-slip sliding tendencies such as that which is often found in automatic transmission clutching surfaces.

In preparing lubricant compositions with amine salts of this invention it has been found that an amount of additive can vary over a wide range such as that of from 0.01% to about 10%, by weight, of the composition and preferably from about 0.1% to about 3%, by weight, of the composition. In preparing lubricant compositions a wide variety of both mineral oil and synthetic base stocks, including mixtures of the same, can be used. Suitable mineral oil base materials include 100 and 200 neutral oils, light and heavy intermediate mineral oils, bright stock as well as combinations of the foregoing. If a synthetic base material is used, it can be that of diesters, polyesters, silicones, silicates, fiuorocarbons, phosphates and the like.

Illustrative of novel amine salts of this invention, there can be mentioned: titanium bis [di(Z-ethylhexyl) orthophosphate] bis [mono (cocoammonium) mono (2-ethylhexyl) orthophosphate]; hafnium tetra [mono (laurylammonium) mono (Z-ethylhexyl) orthophosphate]; Zirconium tetra [mono (laurylammonium) mono (Z-ethylhexyl) orthophosphate]; zirconium tetra [mono (oleylammonium) mono (2-ethylhexyl) orthophosphate]; zirconium tetra [mono (propylammonium) rnono (4octylphenyl) orthophosphate]; amine adduct of N-oleyl-1,3- propylene diamine and Zirconium bis [di(Z-ethylhexyl) orthophosphate] bis [monoacid mono (Z-ethylhexyl) orthophosphate]; amine adduct of hexamcthylenediamine and titanium tetra [monoacid mono (8-phenyloctyl) orthophosphate]; amine adduct of ethylenediamine and titanium bis [di(isobutyl) orthophosphate] bis [monoacid mono (isobutyl) orthophosphate]; titanium (IV) mono [laurylammonium mono (Z-ethylhexyl) orthophosphate] tri [di(Z-ethylhexyl) orthophosphate]; titanium bis [di(2- ethylhexyl) orthophosphate] bis [mono (oleylammonium) mono (Z-ethylhexyl) orthophosphate]; titanium bis [di(Z-ethylhexyl) orthophosphate] bis {mono (laurylammonium) mono (Z-ethylhexyl) orthophosphate]; titanium bis [di(Z-ethylhexyl) orthophosphate] bis [mono (stearylammonium) mono (2 ethylhexyl) orthophosphate]; titanium tri [mono (dioctylammonium) mono (4 octylphenyl) orthophosphate]; [di(4 octylphenyl) orthophosphate]; titanium tetra [mono(oleylammonium) mono(2-ethylhexyl) orthophosphate]; titanium tetra [mono(4-isopropylcyclohcxylammonium) mono (Z-ethylhexyl) orthophosphate]; titanium tetra[mono(oleylammonium) mono (oleyl) orthophosphate]; titanium tetra [mono('oenzylammonium) mono (eicosyl) orthophosphate]; titanium tetra[mono(benzylarnmonium) mono (2,4-dimethyl 4 ethylheptyl) orthophosphate]; titanium tetra [mono(oleylamrnonium) mono (cycloheptyl) orthophosphate]; titanium (IIl) tri [mono (laurylammonium) mono (2-ethylhexyl) orthophosphate]; zirconium (III) tri [mono(oleylammonium) mono (Z-ethylhexyl) orthophosphate]; the amine adduct of triethylenediarnine and titanium tetra[monoacid mono(cetyl) orthophosphate]; titanium (IV) tri[mono(decylammonium) mono (naphthyl) orthophosphate] mono [di(naphthyl) orthophosphate]; hafnium tri[mono(oley1ammonium) mono (benzyl) orthophosphate]; titanium (IV) mono(palmitylarnmonium) mono (linoleyl) orthophosphate] tri [di(linoleyl) orthophosphate]; piperazine adduct of hafnium [monoacid mono(4-isopropylphenyl) orthophosphateh; the diethanolamine adduct of titanium tri[monoacid mono(3,4dipropyleicosyl) orthophosphate]; the aniline adduct of titanium tetra[monoacid mono(oleyl) orthophosphate]; the 1,4-phenylenediamine atlduct of titanium bis[monoacid mono(3-isopropylcyclohexyl) orthophosphate] bis [di(3-isopropylcyclohexyl) orthophosphate].

The following examples are illustrative of the invention:

EXAMPLE 1 Two hundred grams of a mixture of orthophosphates containing 71.7% of mono (2ethylhex.yl) diacid orthophosphate and 28.3% of di (2-ethylhexyl) monoacid orthophosphate were added to 23.6 ml. of titanium tetrachloride in 250 ml. of heptane during fifteen minutes. The mixture was heated with stirring at about 200 F. while blowing with air to remove HCl. The mixture was held at about 200 F. for four hours and overnight with stirring and air bubbling very slowly through the mixture which appeared to be a solution. In the morning air bubbling was increased and continued for one half hour.

The heptane solvent was removed under vacuum. The

product was a mixture of various titanium compounds having 4 moles of phosphate per mole of titanium such as those of the following formulae wherein CgHlq is Z-ethylhexyl:

One hundred grams of the mixed product of Example 1 was neutralized to form a salt with 107.5 grams of Alamine 11, a commercial oleylamine, in 69 grams of toluene by simply admixing the ingredients at about 100 F. The salt was soluble in toluene. Also, 100 grams of the mixture of Example 1 were neutralized to form a salt with Diam 11, oleyl-l,3-propylenediamine, in 54.7 grams of toluene. The amine salt was soluble in toluene.

EXAMPLE 3 By following the procedure of Example 1 but substituting the stoichiometric equivalent quantity of zirconium tetrachloride for titanium tetrachloride there can be produced the corresponding Zirconium derivatives, e.g. zirconium tetra[monoacid mono (Z-ethylhexyl) orthophosphate]; zirconium tri[monoacid mono (Z-ethylhexyl) orthophosphate] mono[di(2-ethylhexyl) orthophosphate]; zirconium bis[di(2 -ethylhexyl) orthophosphate] bis [monoacid mono (Z-ethylhexyl)orthophosphate]; and the like. Also the amine salts of the zirconium compounds can be prepared by simply substituting the stoichiometric equivalent quantity of the mixed reaction products as described hereinabove for zirconium in place of those of titanium in Example 2.

EXAMPLE 4 By following the procedure of Example 1 but substituting the stoichiornetric equivalent quantity of other hydrocarbyl phosphates in place of the Z-ethylhexyl such as those of n-dodecyl, phenyl, benzyl, 3 butyltetradecyl, and 4-octylphenyl, the corresponding titanium compounds with the enumerated hydrocarbyl groups can be produced which can be further reacted with various amines such as oleyl amine to produce the amine salts.

EXAMPLE 5 A mixture of phosphates (500 gm.) containing 445 gm. of (Z-ethylhexyl) diacid orthophosphate and 55 gm. of di(2-ethylhexyl) monoacid orthophosphate were added by means of a separatory funnel over a period of seventeen minutes to 62 ml. of titanium tetrachloride dissolved in 500 ml. of heptane. After eight minutes the product was in the form of an orange colored gel. When all of the phosphate had been added heat was applied and nitrogen bubbled through the solution to carry off HCl. After 45 minutes all of the gel was dissolved. Heating was continued for three hours under reflux and then the solution allowed to stand overnight. The solution was then reheated and blown for two hours with nitrogen. The major reaction product was titanium tetra [monoacid mono (2- ethylhexyl) orthophosphate] and there were minor quantities of similar product wherein some of the phosphate groups contained two mono (Z-ethylhexyl) groups. The solution was then neutralized with Alamine 11 (a commercial oleyl-amine). The neutralization point was determined by titration of a sample dissolved in ASTM naphtha to the p-nitrophenol in methanol end point.

EXAMPLE 6 Mixed phosphates (75 gm.) containing 8.25 gm. of di(2-ethylhexyl) monoacid orthophosphate and 66.75 gm. of mono(2-ethylhexyl) diacid orthophosphate dissolved in 100 ml. of heptane were added by means of a separatory funnel to 9.45 ml. of titanium tetrachloride in 100 ml. of heptane. An orange colored gel formed during the first half of the addition and most of the HCl was formed at that time. As more phosphate was added the gel dissolved. After refluxing for fifteen minutes nitrogen was passed through the solution and the refluxing was continued for 2 /2 hours. Heat was cut off and nitrogen bubbling continued for thirty minutes. The reaction mixture having as its major reaction product titanium tetra mono (Z-ethylhexyl) monoacid orthophosphate was brought to the neutral point with oleyl amine using p-nitrophenol indicator in order to produce the amine salt.

EXAMPLE 7 A mixture of phosphates (50 gm.) containing 89.5% of (2-ethylhexyl) diacid orthophosphate and 10.5% of di(2-ethylhexyl) monoacid orthophosphate was dissolved in 100 ml. of substantially anhydrous heptane. Titanium tetrachloride (9.4 ml.) was added to the dry heptane and the solution added to the dry hot phosphate solution with stirring. This was refluxed for 1% hours with N bubbling through the solution. The solution was then allowed to stand overnight and subsequently refluxed for an additional four hours. It was then cooled and transferred to a 250 ml. graduate. The product so produced was a mixture of titanium tetra [monoacid mono (Z-ethylhexyl) orthophosphate]. This product was neutralized with diethanolamine to prepare a water soluble salt having as its main constituent titanium tetra [mono (diethanolammonium) mono (Z-ethylhexyl) orthophosphate].

EXAMPLE 8 A mixture of phosphates (80.5 gm.) containing, by weight, about 89% of (Z-ethylhexyl) diacid orthophosphate and about 11% of di(2-ethylhexyl) monoacid orthophosphate was dissolved in 100 ml. of heptane and added with stirring to 10.4 ml. of titanium tetrachloride and 100 ml. of heptane. The solution was refluxed for 3 /2 hours while blowing with nitrogen to remove HCl. The titanium [monoacid mono (2-ethylhexyl) orthophosp'nate]. produced was neutralized with 70.1 gm. of cocoamine, and the solvent removed under vacuum. The product was an amber colored viscous liquid with a slight haze. The yield was 153.8 gm.

EXAMPLE 9 A mixture of phosphates (50 gm.) containing about 44.5 gm. of (Z-ethylhexyl) diacid orthophosphate and about 5.5 gm. of di(2-ethylhexyl) monoacid orthophosphate and 100 ml. of isooctane were added to 6.3 ml. of titanium tetrachloride in ml. of isooctane. The solution was heated under reflux for 3.5 hours with nitrogen bubbling through the solution to remove hydrochloric acid. The solution contained a mixture of titanium tetra [monoacid mono (Z-ethylhexyl) orthophosphate], together with other titanium orthophosphates having both 2-ethylhexyl and acid groups. The solution was neutralized with 34.2 gms. of oleyl-1,3-propylene diamine to form the amine salts of the mixed titanium orthophosphates. The desired product was recovered by distilling off the solvent under reduced pressure.

EXAMPLE 10 Dissolved a mixture of orthophosphates composed of 44.5 gm. of mono (Z-ethylhexyl) diacid orthophosphate and 5.5 gm. of di(2-ethylhexyl) monoacid orthophosphate in ml. of isooctane and added it to 6.3 ml. (10.87 gm.) of titanium tetrachloride dissolved in 60 ml. of isooctane. Large amounts of HCl were evolved and a solid material formed which redissolved in the solvent. This solution was heated under reflux with nitrogen bubbling through the solution for 3.5 hours until only a trace of I-iCl could be detected with litmus in the gas stream. The solution contained a mixture of titanium phosphates including substantial quantities of titanium tetra [monoacid mono (Z-ethylhexyl) orthophosphate] and a lesser quantity of titanium bis [di(Z-ethylhexyl) orthophosphate] bis [mono(2-ethylhexyl) monoacid orthophosphate]. Di(2-ct'nylhexyl) amine (5L2 gm.) was added to the reacting mixture. The isooctane solution of the amine salt of the titanium hydrocarbyl acid phosphates was water washed and the isooctane removed under vacuum. The product was a clear yellow viscous liquid.

9 EXAMPLE 11 Following the procedure of Example there was added 40.5 gm. of Prirnene 81R, a commercial form of tetra decyl amine to the reaction mixture and the solution washed twice with hot salt water, filtered to dry and the isooctane was removed under vacuum. The product was a clear almost colorless viscous liquid. The yield was 92.5 gms.

EXAMPLE 12 One hundred ml. of heptane were chilled and there was added to it 6.28 ml. (10.86 gm.) of titanium tetrachloride. Fifty gm. of a cooled mixture of mono (2-ethylhexyl) diacid orthophosphate (89%) and di (Z-ethylhexyl) monoacid orthophosphate (11%) in 50 ml. of heptane were added to the titanium tetrachloride solution. The beaker which contained the phosphate was rinsed with an additional 50 ml. of heptane. The solution was heated under reflux for four hours. The largest single constituent of the refluxed product was titanium tetra [monoacid mono (2-ethylhexyl) orthophosphate]. Fifty-eight and one-half gram of oleyl aimine were added and the heptane removed under vacuum. The product was a clear yellow viscous liquid. The largest single constituent of the prod not was the oleyl amine salt of titanium tetra [monoacid mono (2-ethylhexyl) orthophosphate].

EXAMPLE 13 Mixed monoand di-isooctyl acid phosphates (25.76 gm.) containing 14 gm. of mono(2-ethylhexyl) diacid orthophosphate and 11.33 gm. of di (Z-ethylhexyl) monoacid orthophosphate were admixed with 25 ml. of heptane and the mixture was added to 3.794 gm. (2.2 ml.) of TiCl; in 50 ml. of heptane. The mixture was heated under reflux while blowing with N for three hours. The solvent was removed under vacuum to give a white gelatinous material. This material was neutralized with 18.5 gm. of di (Z-ethylhexyl) amine, diluted with pentane, and washed three times with water. It was then dried and pentane was removed.

EXAMPLE 14 Mono (Z-ethylhexyl) diacid orthophosphate 84.0 gm. is dissolved in 200 ml. of toluene and added to 19 gm. of TiCL; dissolved in 150 ml. of toluene. The mixture was heated under reflux with nitrogen bubbling therethrough for four hours. The product in the reaction mixture is titanium tetra[mo-no(2-ethylhexyl) monoacid orthophosphate]. A portion of the reaction mixture containing 8.8 gm. of the product can be neutralized with 2.5 gm. of oleyl amine to produce titanium tetra[mono(oleylammonium) mono(2-ethylhexyl) phosphate]. Following the above procedure the corresponding amine salts can be prepared by simply substituting the stoichiometric equivalent quantity of isopropylamine, aniline, n methyl cyclohexylamine, isopropanolamine, 6-hydroxyhexylamine, or 12-hydroxydodecylamine.

EXAMPLE 15 Following the procedure of Example 14 in the preparation of titanium tetra[monoacid mono (Z-ethylhexyl) orthophosphate] there can be produced titanium tetra [(monodecyl monoacid orthophosphate)]; titanium tetra [mono (3-butyldodecyl) monoacid orthophosphate]; titanium tetra[(monophenyl monoacid orthophosphate)]; and titanium tetra[mono(4-octylphenyl) monoacid orthophosphate]; by substituting for the mono (Z-ethylhexyl) diacid orthophosphate the stoichiometric equivalent quantity respectively of monodecyl diacid orthophosphate; mono(3-butyldodecy1) diacid orthophosphate; monophenyl diacid orthophosphate; and mono (4-octylphenyl) diacid orthophosphate.

EXAMPLE 16 Titanium trichloride (15.3 gm.) in 100 ml. of benzene were admixed with 63 gm. of mono (Z-ethylhexyl) diacid orthophosphate dissolved in 150 ml. of benzene. The mixture is heated at about C. to form a solution containing titanium tri[mono(2-ethylhexyl) monoacid orthophosphate]. This titanium compound dissolved in the reaction mixture is neutralized with 30 gm. of hexylamine to prepare titanium tri[(monohexylarnmoniu.m mono (2-ethylhexyl) phosphate].

EXAMPLE 17 This example together with Table 1 shows tests for icing inhibition in a spark ignition engine by the use of gasoline compositions containing additives of this invention. A single cylinder engine was operated at constant speed with inlet air conditions controlled to promote carburetor icing. Test conditions were chosen to give an increase in manifold vacuum of 2.5 inches of mercury in 20 seconds with the base fuel. A glass or clear plastic carburetor throttle body was used so that ising could be confirmed by visual inspection when desired. The base fuel was a mixture in equal parts by volume of isooctane and precipitation naphtha. Anti-icing was determined by noting the increase in time necessary to obtain a manifold vacuum of 2.5 inches of mercury by use of the base fuel (gasoline) containing an amine salt of this invention as compared to the base fuel without such an amine salt. The results of these tests wherein the time required for obtaining the specified vacuum is referred to as stall time are given in Table 1. In Table 1 additive A is titanium tetra[mono (oleylammonium) mono (Z-ethylhexyl) orthophosphate]; additive B is titanium tetralmonoacid mono (Z-ethylhexyl) orthophosphate] wherein the free acid groups were neutralized with Noleyl-1,3-propyleue diamine; and additive C is titanium tetra[mono(1aurylam monium) mono (Z-ethylhexyl) orthophosphate].

TABLE l.-GASOLINE ANTI-ICING ACTIVITY Concentration 01' Percent Improvement Additive Additive in p.p.n1. in Stall Time Over Base Fuel EXAMPLE 1% This example, together with Table 2 shows that gasoline compositions containing amine salts of this invention have carburetor detergency. A single cylinder engine, modified to greatly increase blowoy, was operated at a part throttle, constant speed condition for 20 hours for each test. The engine was equipped with a blowby loop which returned blowby from the push rod cover to the air inlet side of the carburetor. The carburetor was disassembled after each test and visually merited by examining the top and bottom of the throttle plate and the venturi top and bottom. The gasoline compositions used in each test except for the base fuel which did not contain an additive contained 50 ppm. (parts per million) by weight of an additive of this invention. in Table 2, under the designation Composition, the different letters refer to test base fuel containing: titanium tetra [monoacid mono (2-ethylhexyl) orthophosphate] wherein the free hydroxyl groups were neutralized with N-oleyldfi-propylene diamine and which is designated as A; titanium tetra [mono (oleylammonium) mono (Z-ethylhexyl) orthophosphate] which is designated as B; titanium tetra [mono (laurylammonium) mono (2-ethylhexyl) orthophosphate] which is designated as C; titanium tetra [monoacid mono (Z-ethylhexyl) orthophosphate] wherein the hydroxyl groups were neutralized with a mixture of primary branched chain alkylamines containing from 12 "i l. to 14 carbon atoms (Primene 81R). The results of these tests are shown in Table 2 wherein the merit rating of 10 represents clean whereas a merit rating of represents black heavy deposits.

TABLE 2.CARBURETOR DETE RGENCY Percent Improvement Composition Over Base Fuel Merit Rating Base Fuel A EXAMPLE 19 open throttle and 1050 r.p.m. until 150 hours are accumu- 2 latecl for each test composition. The engine is equipped with a blowby loop which returns blowby from the push rod cover to the air inlet side of the carburetor. The intake system is disassembled after each test and visually merit rated for cleanliness in the carburetor, intake manifold, and intake valve area. The results of a series of tests for intake system cleanliness appear in Table 3. Composition A in the table represents the base fuel containing 50 p.p.m. of titanium tetra [mono (oleylamrnonium) mono (2-ethylhexyl) orthophosphate]; Composition B represents the base fuel containing 50 p.p.m. of titanium tetra [mono (laurylammonium) mono (2-ethylhexyl) orthophosphate]; and Composition C represents the base fuel containing 50 p.p.m. of titanium tetra[monoacid mono (Z-ethylhexyl) orthophosphate] wherein the acid groups are neutralized with a mixture of primary branched chain alkyl amines having from 12 to 14 carbon atoms.

TABLE 3.INTAKE SYSTEM CLEANLINESS TEST Composition Merit Rating Percent Improvement (Glean=l00) Over Base Fuel lluso Fuel 36 A '70 94 75 108 72 100 68 S8 EXAMPLE 20 This example taken with Table 4 shows that the additives of this invention in base fuel (gasoline) reduce surface ignition of a spark ignition engine. A single-cylinder engine, equipped with an ionization gap to count flame fronts occurring before or after the normal flame, was operated at 1000 r.p.m. with the throttle cycled 50 seconds at idle and 250 seconds at wide open for 8 hours for each test. The average hourly surface ignition count for the last 4 hours of each test composition was compared to that of the base fuel without additive and reported on a percent reduction basis. The additive employed in these tests was titanium tetra[m0no(0leylan1- monium) mono (Z-ethylhexyl) orthophosphate]. The results of the tests are shown in Table 4.

12 EXAMPLE 21 This example taken with Table 5 shows the reduction in octane requirement increase of base fuel (gasoline) containing an additive of this invention as compared to the base fuel without the additive. A V-8 passenger car engineusing base fuel or base fuel plus an additive of this invention, modified to increase blowby, is cycled for 50 seconds at no load idle and 250 seconds at a medium load, moderate speed condition for 125 hours for each test. The engine is equipped with a blowby loop which returns blowby from the rocker arm cover to the air cleaner. The octane requirement of the engine at wide open throttle and 1000 rpm. is determined every 24 hours during the 125 hour period of the test. Octane requirements are plotted against test hours. The octane requirement increase for each test composition is calculated from the hour requirement read from the curve minus the zero hour requirement. The results of a series of such tests are shown in Table 5 wherein the additives were used in a concentration of 50 p.p.m. in the base fuel and wherein: A designates titanium tetra[mono (oleylammonium) mono (Z-ethylhexyl) orthophosphate]; B designates titanium tetra [monoacid mono(2-ethylhexyl) orthophosphate] wherein the acid groups were neutralized with N-oleyl-1,3-propylene diamine; and C designates mixed primary amines of branched chain alkyls having from 12 to 14 carbon atoms.

REQUIRUDMENT IINCRE'ASE Percent reduction in octane requirement increase from Additive: base fuel EXAMPLE 22 A gasoline composition affording rust inhibition, 9. re-

duction in octane requirement increase, protection against carburetor deposit build up, suppression of surface ignition, and inhibition of carburetor icing can be prepared by dissolving titanium tetra[mono(oleylammonium) mono (Z-ethylhexyl) orthophosphate] in gasoline wherein the amine adduct is employed in a concentration of one pound for each 3,000 gallons of the composition.

EXAMPLE 23 Another suitable composition is that of a suitable base gasoline containing 100 p.p.m. by weight of titanium tetra[mono (laurylammonium) mono (Z-ethylhexyl) orthophosphate].

EXAMPLE 24 Another suitable composition can be prepared by dissolving two pounds of titanium bis[di(2-ethy1hexyl) orthophosphate] bis[rnono (oleylammonium) mono (2- ethylhexyl) orthophosphate] in 3,000 gallons of gasoline.

EXAMPLE 25 EXAMPLE 27 Titanium bis[di(2-ethylhexyl) orthophosphate] bis [monoacid mono (Z-ethylhexyl) orthophosphate] is obtained from the reaction of 2 moles of phosphate pentoxide and one mole of titanium tetrachloride with 6 moles of 2-ethyl-l-hexanol as shown below:

wherein R is 2-ethylhexyl.

To a suitable reaction vessel equipped with a mechanical stirrer, stoppered pressure equalizing addition funnel, thermometer, gas inlet tube, and a reflux condenser protected with a drying tube, there were added 400 ml. of anhydrous n-heptane and 71.0 g. (0.5 mole) of phosphorus pentoxide. With the stirrer going at a rate to insure a uniform dispersion, 47.4 g. (0.25 mole) of titanium tetrachloride was added next. Finally 215 g. (1.65 moles) of 2-ethyl-1-hexanol, contained in the pressure equalizing addition funnel, was run into the reaction vessel at a rate such that the temperature of the reactants did not rise above 60 C. When this step was completed, the solution was homogeneous. The reactants were then heated at 98-103 C., and when evolution of hydrogen chloride moderated, dry air was passed through the solution to displace the acid gas more rapidly and to accelerate the reaction. When further evolution of hydrogen chloride wase no longer observed, as revealed by Congo red indicator, the n-heptane and any unreacted octanol were removed by distillation in vacuo. The final temperature of the residual product in the reaction vessel was 175 at 25 mm. A very pale yellow syrupy product was obtained weighing 275 g. which is 99% of theory based on the metal halide. Inspection data were as follows:

Calculated formula Weight for What is claimed is:

1. A lubricating composition comprising; a major quantity of a lubricant and a minor quantity, sufficient to impart wear resistance to the composition, of an organic amine salt of an acid phosphate of the formula:

wherein each R is a hydrocarbon, (n) is an integer from 1 to 4, (n') is an integer from 0 to 3 and the total of (n) and (n) is equal to the valence of the metal M, said organic amine having from 1 to about 30 carbon atoms.

2. A composition of claim 1 wherein the amine has from about 6 to about 24 carbon atoms.

3. A composition of claim 2 wherein the amine is hydrocarbyl aliphatic amine.

4. A lubricating composition comprising a major quantity of mineral oil and a minor quantity of an additive dissolved in said mineral oil sutficient in quantity to provide wear resistance properties to the oil, said additive being an amine salt of a compound of the formula:

wherein each R is a hydrocarbyl of from about 6 to about 22 carbon atoms, M is a metal of Group IV E of the Periodic Table, (n) is an integer from 1 to 4, and (n) is an integer from 0 to 3 and the total of (n) is equal to the valence of the metal M, said amine being an organic amine having from 1 to about 30 carbon atoms.

5. A composition of claim 4 wherein the metal has a valence of 4 and the amine has from about 6 to about 24 carbon atoms.

6. A composition of claim 5 wherein the amine is an alkylamine.

7. A composition of claim 6 wherein M is titanium, each of (n) and (n') is 2, each R is 2ethylhexyl and the amine is cocoamine.

8. A composition of claim 5 wherein (n) is 4 and (n') is 0.

9. A composition of claim 8 wherein the amine is aliphatic amine and each R is branched chain hydrocarbon.

References Cited UNITED STATES PATENTS 3,231,347 1/1966 Revukas 44-69 3,275,668 9/1966 Revukas 260429.3 3,297,573 1/1967 Hain et a1. 252-325 3,334,978 8/1967 Revukas 4469 3,346,492 10/1967 Hess 252-325 DANIEL E. WYMAN, Primary Examiner.

PATRICK P. GARVIN, Examiner. 

